Treatment of hydrocarbon oils



July v13, 1931.v

Patented July A13, v1937.

UNITED i STATES PATENT OFFICE -v This invention relates to a process for the catalytic treatment of lhydrocarbons and relates particularly to a process for catalytic desulfurization of petroleum hydrocarbons.Y

In \a 'previous application Serial No. 632,608

filed September`10, 1932 of which I am co-inventor'there is described a -process for the catalytic desulfurization of petroleum hydrocarbons Awhich comprises passing petroleum vapors containing objectionable sulfur compounds over a desulfurization catalyst, namely bauxite, at tem-.-

peratures specifically suited to eiect decomposition of the sulfur compounds to hydrogen sulfide and followed by removal of the hydrogen sulde.

I now propose to eiect an improvement in this process whereby more efficient desulfurization is effected and the life of the catalyst markedly prolonged. v Y g I have found that in carrying out the above process, the catalyst when acting upon petroleum l fractions, particularly those containing unsaturated constituents-will belrendered ineffective in a comparatively short die tol-it @ecomng contaminated by polymersffirmed`frm` unsat urated constituents in the petroleum -vapors and 'by carbonaceous matter formed probably as a result of the decomposition of sulfur compounds.

I therefore propose to increase the ective life U0 so as toremove a major portion of those constituents which will form`polymers and contaminative carbonaceous matter when brought in contact with the. catalyst.

` "`phenyLsulfldejfalso,is less readily decomposed gL-advantagej-:of then great difference in 1 lity"oftthese sulfur compounds itis possible by-the .proc disclosed herein to obtain much of the catalyst by pretreating the hydrocarbons As mentioned briefly above, I have :Ifoundth'at pletelydecomposed than dimethyl sulfide.v Dii `than the; aliphatic suldes except methyl. By

.thatfiused more'ilicient and complete removal of the` sulfur from the petroleum loil;

Prior to this discovery it has 'been the practice toV pass the petroleum vapors over the bauxite r ,catalyst at a temperature suiciently high to d breakdown the major' part 'of these sulfur compounds. Ffor a short time with a fresh-catalyst the activity .was sufficientlyA high so that the less readily decomposable compounds such as the dimethyl sulfide and diphenyl sulfide were at- 10- tacked, but asthe catalyst becamecontaminated with carbonaceous matter resulting from the decomposition of the sulfur compoundsv and polymerization of the highlyi unsaturated hydro- 15 carbons the 'catalyst decreased in activity with the-result that the more stable sulfur compounds were untouched. It became necessary then .to raise the temperature still higher to compensate for the loss in activity of the catalyst, and this increase in temperature, of course, caused thezo rate offormation of carbonaceous matter to be speeded up, thereby accelerating the rate of loss of activity. vvI have found now that the aforementioned diiiiculties canbe avoided by operating in the manner disclosed below. 25 In my process' the petroleum vapors are treated catalytically in two steps. In the first step the vapors are passed over a bauite catalyst at temperatures sufficiently high to decompose the more readily ,decomposable sulfur compounds.

The carbnaceous residues from this decomposition together with the polymeric bodies formed 'from the highly unsaturated hydrocarbons are deposited in the catalyst bed., After an extended period of operation, depending on the stock being treated, the amount of liquid and tarry deposition maybe suicient to collect at the bottom of the'catalyst bed from which it may be drained.

In order to remove any entrained high boiling' polymeric material from the. treated vapors, they 40 may be passed through a polymer separator prior to the second Icatalytic step. By removing from the vapors a major portion y' of the carbonaceous forming constituents in the first step, the catalyst in the second stepis then permitted to act more exclusively as a desulfurizing agent for the more stable sulfur ogmpou'nds and its activity for this purpose is thus heightened and prolonged.

The preferred temperatures for this two step operation are 60G-'700 F. for the rst step and G50-800 F. fortl`1e second step. It has .been found advantageousto maintain the temper'af ture in the .second step somewhat 4higher than -in the first step so that-the vapors are above their dew-point and the catalyst is maintained as free aslpossible of liquid particles which intime tend to form carbonaceous residues. In such operation the vapors coming from the polymer separator are superheated some 25 to 50 degrees Fahrenheit above that in the first catalyst chamber.

After the second catalyst treatment the hydrogen sulfidefis removed from the treated vapors by any'of the usualI methodsksuch as (1) fractionation, or (2) extraction with alkali.

I have also found that when the second step catalyst begins to lose effectiveness for decomposing the less readily decomposable sulfur compounds it will still retain considerable effectiveness .toward the more-readily decomposable sulfur compounds as well as suitable efficiency as a polymerizing agent toward unsaturated materials.

I therefore am enabled to'effect'additional econo' mies in my process by using the second step catalyst as the first step catalyst when it begins to lose effectiveness tow rd the less-readily decomposable sulfur comp unds, and I can thus obtain an extended period of .usefulness from such catalyst.

Other objects `'and advantages of my new inveny tion will be apparent from the lfollowing detailed description taken in conjunction with the attached drawing which illustrates a diagrammatic form of apparatus for successfully practicing the invention. 1

s Referring to the drawing petroleum hydrocarbons to be desulfurized Will be fed through pipe I in which is mounted apump 2 and Will'be pumped thereby through a, heating coil 3 which is mounted in a furnace 4. From the furnace 4 the hydrocarbons will pass through a pipe '5 in which lis mounted a valve 6 into acatalyst chamber 1, in which is maintained a bed of catalytic material such as bauxite. The hydrocarbons in passing through the heating coil 3 will be heated by gases of combustion generated inthe furnace 4 to such a temperature as to effect substantially complete vaporization of the hydrocarbons. 'I'he temperature will be sufficiently high-so that the more readily decomposable sulfur compounds contained in the vapors will be decomposed bythe action of the bauxite which lwill at the same time effect polymerization of the highlyunsaturatedhydrocarbons contained in the vapors and other polymer or gum forming material formed as a result of the decomposition of the sulfur compounds. The vapors will`be constrained to pass through the body of catalyst contained in chamber 'I and the catalyst `will be maintained substantially at the temperature of the vapors by the heat of the vapors themselves. Catalyst chamber 1 will be suitably insulated to reduce heat losses therefrom to a minimum. 'j

From catalyst chamber I the treated vapors and polymeric liquid will pass through a pipel 8 in which is mounted a valve 9 intoa polymer separator II wherein the polymers will be separated from the treated vapors. Polymer separator I I may be a simple separator or `a fractionating tower or any other similar device which will effect a suitable separation of vapors frbm polymers and other liquid constituents. The polymers and other liquid constituents will be Withdrawn from polymer separato I I vthrough a-pipe I2 in which is mounted a valve I3, the manipulation of which will'control the 'rate of Withdrawal of polymers from the system. The` vapors freed from the major portion of polymer forming materials and less refractory sulfur compounds and ture substantially above that to which the origi,'

nal material was heated in coil 3. These higher temperature vaporswill be constrained to pass through the catalyst in chamber 20 wherein theV catalyst will act' upon the vapors to decompose l the more refractory sulfur compounds remaining in the vapors. The bed of catalyst in chamber 20 will be maintained at the higher temperature Jrequired'by the vapors themselves, this chamber also being suitably insulated to reduce heat losses to a minimum. The treated vapors containing hydrogen sulfide which is the principal decomposition product of sulfur compounds will pass from chamber 20 through apipe 2I in which is mounted a valve 22'through a condenser 23 wherein the hydrocarbons will be condensed together with hydrogen sulfide some of which may remain uncondensed. The mixture of condensate and uncondensed hydrogen sulfide will then pass from condenser23 through a pipe 24 into a separator 25 wherein the hydrogen sulfide will be separated from the desulfurized hydrocarbons.`

The hydrogen sulfide may be separated from the hydrocarbons by fractionation and will be vented from separator 25)v through a pipe 26 in which is mounted a valve 21,. The desulfurized hydrocarbons will be withdrawn from separator 25 to s torage through a pipe 28 in .which is mounted a valve 29. j

Instead of effecting a physical separation of hydrogen sulfide from the desulfurized'hydrocarbons, the hydrogen sulfide may be removed by a' chemical agent as for example caustic soda solution or the like. If the chemical method' is used, the hydrogen sulfide removing agent may be fed through a pipe 30 into pipe 2I ,at a point preceeding condenser 23 and it will neutralize and Ldissolve the hydrogen sulfide en route to sepa- `rator 25. The desulfurized hydrocarbons and the solution ofhydrogen sulfide in the removing agent will then be separated from each 4other either in separator 25 or by any suitable conventional means, depending upon the particular nature of the hydrogensulde removing agent.

It will be understood that removal of hydrogen sulfide from the treated hydrocarbons by chemical means may be 4effected after the condensation instead of before as shown. For example the liquid hydrocarbons containing hydrogen sulfide may be washed 'with a suitable chemical in separator 25 or in apparatus subsequent to separator 25,I such methods being Well known in the art.

' The process may be operated at a pressure, that is sufficient only to overcome the pressure drop- 'through the apparatus or it'may`I be operated at substantial superatmospheric pressure throughout, in which case valve 21 may be manipulated to lontrol the pressure on the system, or the initial scribed, until thenew catalyst in chamber 'I begins to lose its eiflciency when: the flow through the two chambers 'I and 20 will again be altered in the manner indicated. I am thus enabled to obtain increased efficiency from a single batch of catalyst and may thus effect appreciable additional economics thereby.

Other variations of my new process will be apparent to those skilled in the art andit is my intention to claim all such variations within the scope of my invention as deiined by the appended claims. z

I claim: l 1. The process of desulfurizi'ng hydrocarbon ll,

which comprises passing the said hydrocarbon pors, superheating the resultantV partially de sulfurized vapors, passing said superheated vapors through a second body ofbauxite catalyst maintained at a temperature substantially 'higher than that maintained' in said rst body of catalyst, whereby the less readily 4decomposable organic sulfurvcompounds are decomposed into simpler sulfur compounds, and finally removing the decomposed sulfur compoundlgfrom the treated hydrocarbon oil. g 1* 2. The process of desulfurizing petroleum oil, which comprises passing thesaid petroleum oil in vapor form throughvaflrst body ofbauxite catalyst at a temperature within the range of 600 to 700' F., whereby the more readily decomposable organic sulfur compounds in the petroleum vapors are decomposed by the said catalyst into hydrogen sulfide and whereby the polymer forming constituents which are deleterious to the desulfurization activity of bauxite catalyst arepolymerized and rempved` by condensation from the said petroleum vapors, superheating the resultant partially desulfurized and puried va-v pors to a temperature higher than that maintained in said rslt body of catalyst and pass- -ing saidsuperheated vapors through a second heating the partially desulfurized petroleum vapors and while at a temperature substantially higher than that maintained in said first treating chamber passing the said vapors through a second treating chamber containing bauxite catalyst, whereby less readily decomposable organic sulfur compounds are converted into hydrogen suliide, and finally removing the hydrogen sulfide from the desulfurized petroleum oil.. Y

4. In a process for the catalytic desulfurization of hydrocarbons, wherein said hydrocarbons invapor form are contacted with a desulfurizatioli catalyst consisting of bauxite, the improvement which comprises contacting hydrocarbon vaporswith a first body of bauxite catalyst at a temperature in the range 600 to 700 F. thereby decomposing more readily decomposable sulfur l compounds contained in the said vapors and polymerizing thehighly unsaturated hydrocarbons and tar forming materials in said, vapors, separating resulting polymers and carbonaceous` materials from said vaporsvthen passing the partially desulfurized and purifledvapors in contact with a second body of said bauxite catalyst at a temperature in the range 650 F. to 800 F. to thereby decompose the less readily decomposable sulfur compounds contained in said vapors into hydrogcn sulfide and removing said hydrogen sulfide from tl'ie treated hydrocarbons.'

-5. The improved method of converting organic sulfur compounds in cracked gasoline into hydrogen suliide which comprises passing said cracked gasoline in vapor form in contact with a rst body of bauxite maintained at a temperature within the range of 600 to 700 F., whereby the `more readily decomposable organic sulfur compounds in the cracked gasoline vapors are decomposed by the said catalyst into simpler sulfur compounds and wherebyv the polymer formingconstituents which are deleterious to the desulfurization activity of bauxite catalyst are polymerized, removing the s aid polymers by condensation from the said cracked gasoline vapors, thereafter passingthe resulting partially treatved vapors in contact with a second body of bauxite maintained at a temperature at least F. higher than that maintained inaid rst body of bauxite and iinally removing he decomposed sulfur compounds from the treated cracked gasoline. 1

6. The improved method of converting into `hydrogen sulde the organic sulfurl compounds body of bauxite catalyst without substantial cooling of the superheated vapors, whereby the less readily decomposable organic compounds are converted .into -hydrogen sulde, and nally removing .the hydrogen sulde from the -treated ,-lorganlc sulfunf compounds are converted into containing bauxite catalyst, whereby part of the,

' :hydrogen fs'l'ilildeg` and the tar forming constituents inthe petroleum vapors are polymerized to high boillngcompounds which are condensed to liq'uld' stateon the. bauxite catalyst, then superin a mixture of petroleum fractions'consistlng of gas oil and lighter fractions, which comprisesy passing said mixture'in vapor form in contact with a iirst body of bauxite maintained at a temperature in the range GOO-730 F., whereby the more` readily decomposable organic sulfur compounds in the said vapor mixture are decomposed by the said vcatalyst into simpler sulfur compounds and whereby the polymer forming constituents 4which are deleterious to the desulfurization activity of bauxite catalyst are polymerized, removing the said polymers by condensation from the said vapor mixture, thereafter passing the resulting partially treated vapors in contact with a second bodyof bauxite maintained at a temperature above 730 F whereby the less readily decomposable organic sulfur compounds are decomposed into simpler sulfur compounds, and iinally removing the decomposed sulfur compounds fromJ-the treated mixture ofpetroleum fractions. l

- WALT/ER A..SCHULZE. 

